CN101460549B

CN101460549B - Process to prepare fluoropolymer dispersions and membranes

Info

Publication number: CN101460549B
Application number: CN2007800203292A
Authority: CN
Inventors: R·D·卢森伯格
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 2006-06-01
Filing date: 2007-05-24
Publication date: 2012-06-13
Anticipated expiration: 2027-05-24
Also published as: US20120016044A1; TWI358418B; EP2027191B1; EP2027191A2; DE602007012237D1; JP2009538967A; WO2007142886A2; WO2007142886A3; US8058319B2; CN101460549A; TW200804472A; US20070282022A1

Abstract

Described is a process to prepare fluoropolymer organic-liquid dispersions containing a homogeneous mixture of reacted and unreacted sulfonyl halide groups. The dispersions are useful in the preparation of crosslinked membranes.

Description

Prepare fluoropolymer dispersions and the method for film

Technical field

The present invention relates to the method for preparing fluoropolymer organic liquid dispersion, the fluoropolymer organic liquid dispersion contains the homogeneous mixture of reaction and unreacted sulfonyl halide groups.The dispersion can be used for the film for preparing crosslinking.

Background technology

Electrochemical cell generally includes the anode being separated by an electrolyte and negative electrode, wherein being used as polymer dielectric using PEM (hereafter " PEM ").Usually using metallic catalyst and electrolyte mixture formation anode and negative electrode.The known use of electrochemical cell is to be used for fuel cell (battery that fuel and oxidant are changed into electric energy).Fuel cell is formed usually as membrane electrode assembly (MEA) and the stack or assembly parts of other optional features each including PEM, anode and negative electrode.In this battery, to anode supply reactant or reduction fluid, such as hydrogen or methanol, and oxidant, such as oxygen or air are supplied to negative electrode.Reduce fluid at anode surface electrochemical reaction to produce hydrogen ion and electronics.Electronics is directed to external load circuit, is then return to negative electrode, and hydrogen ion is transferred to negative electrode through electrolyte, and they produce water with oxidant and electron reaction and discharge heat energy herein.

PEM long-time stability are vital to fuel cell.For example, the lifetime goal of static fuel cell applications is operation 40,000 hour, and the life-span of mobile applications requirement at least 10,000 hour.But, common film used can be degraded over time in whole field, so as to endanger MEA durability and performance.For example, stress caused by change in size during as the hydration or dehydration in fuel cell cyclic process is likely to result in creep and ultimately causes film failure.A solution to this problem is that crosslinking is provided in film body.But, due to preparing the difficulty of cross-linking solution or dispersion in the limited solvent or organic liquid medium that can be used together with fluoropolymer electrolyte, some polymer dielectrics of homogeneous cross-link, the ability of such as fluoropolymer electrolyte is restricted.

Solvent or dispersion cast (casting) are common and advantageous fuel cell membrane fabrication process.The well-known fluoropolymer electrolyte dispersions of broad commercial applications are available from E.I.duPont de Nemours and Company, Wilmington DE.

Perfluorinated ion cross-linked polymer.The catalyst ink formulations that manufacture is used to form fuel cell MEA electrode are also commonly used for for forming the solution and dispersion of film.The fluoropolymer electrolyte dispersions for being adapted to cast membrane are disclosed in United States Patent (USP) Nos.4,433,082 and 4,731,263, and they are taught without significant sulfuryl fluoride (SO₂F) sulfonic acid (the SO of concentration₃) and sulfonate radical (SO H₃ ^-) form aqueous organic and organic-liquid fluoropolymer electrolyte dispersion composition.

The SO2F groups that United States Patent (USP) 3,282,875 discloses precursor fluoropolymer electrolyte can be used for making fluoropolymer be crosslinked or " vulcanization " by reacting with difunctionality or polyfunctional crosslinking agent, but without the open method for uniformly realizing this point.United States Patent (USP) No.6,733,914 is disclosed to be incited somebody to action by being reacted with ammoniacal liquor

Figure 2007800203292100002G2007800203292D0001104340QIETU

Birds of the same feather flock together quite a few SO of compound film₂F groups are uneven to change into SO₃ ^-With sulfonamide (SO₂NH₂) group method.The film is then crosslinked by thermal anneal step at high temperature, a portion SO₂NH₂Group estimation can be with residual SO₂F radical reactions formation sulfimide (- SO₂NHSO₂-) crosslinking.Uniform crosslink density can not be provided in whole film with the uneven property of the front reaction of ammoniacal liquor.

Height fluorination or

The SO of-class fluoropolymer electrolyte material₂F precursor forms are not easily dissolved or are dispersed in common organic liquid, but may dissolve in fluorated solvent under certain conditions.But, the cost related to fluorated solvent and environmental considerations may make the extensive solvent that it cannot act as dispersion cast medium.Furthermore, it is possible to and SO₂The crosslinking agent that many of F radical reactions is contemplated that is slightly soluble in fluorated solvent, but may dissolve in common organic liquid.Prepared accordingly, it would be desirable to develop with common non-fluorinated liquid or solvent containing significantly but less than 100% residual SO₂The method simple and easy to apply of the fluoropolymer electrolyte dispersions of F radical concentrations.The dispersion can easily casting film and homogeneous cross-link with fuel cell and similar techniques.

The content of the invention

The present invention relates to the method for manufacture polymeric dispersions, it is comprised the steps of：There is provided comprising polymer solvent and contain SO₂The solution of the polymer of X side bases, the wherein polymer include fluorinated backbone and formula-(O-CF₂CFR_f)_a-(O-CF₂)_b-(CFR’_f)_cSO₂Side base shown in X, wherein X are halogen, R_fAnd R '_fIndependently selected from F, Cl or the perfluorinated alkyl with 1 to 10 carbon atom, a=0 to 2, b=0 to 1, and c=0 to 6；The solution is merged with nucleophilic compound Y and polar liquid to form reactant mixture；And substantially all polymer solvents are removed from reactant mixture to form dispersion by distilling, wherein the SO of about 5% to about 95%₂X side bases with nucleophilic compound Y react and about 95% to about 5% SO₂X side bases keep unreacted.

The invention further relates to prepare the method for film, comprise the following steps：Dispersion is provided according to step just as described above；And film is prepared by the dispersion.

In one embodiment, methods described also includes making the reactant mixture of second step or the dispersion of the 3rd step mix with crosslinkable forming crosslinking between side base.The crosslinking may include one or more sulfonimide moieties.

The invention further relates to be related to the dispersion as made from the above method, and the film prepared by the dispersion.

Embodiment

Herein when listing number range, unless otherwise specified, the scope is intended to include its end points and all integers and fraction within the range.When specifying a scope, it is not intended to limit the scope of the invention to cited concrete numerical value.In addition, all ranges set forth herein is intended to the specific scope for not only including specifically describing, also include any combinations of numerical value therein, including listed minimum and maximum value.

Fuel cell is the electrochemical appliance that the chemical energy of fuel (such as hydrogen) and oxidant (such as air) is changed into electric energy.Fuel cell is formed usually as each stack or assembly parts including electrolyte, the membrane electrode assembly (MEA) of anode (electronegative electrode) and negative electrode (electrode of positively charged) and other optional features.Often polymeric proton exchange membrane (PEM) is used as electrolyte.Fuel cell, which is generally also included, to be made electrical contact with each electrode and allows reactant to be diffused into electrode and the porous, electrically conductive sheet referred to as gas diffusion layers, gas diffusion substrate or gas diffusion backing.When being coated with elctro-catalyst on PEM, MEA is said to be including catalyst coated membrane (CCM).In other cases, when being coated with elctro-catalyst on the gas diffusion, MEA is said to be including gas-diffusion electrode (GDE).The functional part of fuel cell is generally as follows aligned in layers：Conductive plate/gas diffusion backing/anode/membrane/negative electrode/gas diffusion backing/conductive plate.

The film being made by dispersions described herein and by method described herein, can be with being combined especially when changing into ionomeric acid form using PEM fuel cell.Example includes hydrogen fuel cell, reformed hydrogen fuel cells, DMFC or other organic/air (for example with ethanol, propyl alcohol, dimethyl ether or diethyl ether, formic acid, carboxylic acid systems such as acetic acid and analog).The film is also advantageously utilised in the MEA of electrochemical cell.Other purposes of film as described herein and method are included in battery pack and other types of electrochemical cell using and being used in battery for water electrolysis formation hydrogen and oxygen.

PEM is generally by ion-exchange polymer, and also referred to as ionomer is constituted.According to the practice of this area, term " ionomer " is used to represent the polymeric material with the side base containing terminal ionic group.Terminal ionic group can be the acid or its salt being likely encountered in the interstage of processing or the manufacture of fuel cell.It is sour form that the appropriate operation of electrochemical cell, which may require ionomer,.Highly fluorinated ionomer is often used in PEM.The present invention relates to available for the method for manufacturing some such highly fluorinated polymers.

One aspect of the present invention, which is related in non-fluorinated liquid, contains a considerable amount of and dispersed sulfonic acid halide (SO₂X) the manufacture method of the polymeric dispersions of group.This method comprises the following steps：

A) provide comprising polymer solvent and contain SO₂The solution of the polymer of X side bases, the wherein polymer, which are included, contains formula-(O-CF₂CFR_f)_a-(O-CF₂)_b-(CFR’_f)_cSO₂The fluorinated backbone of side base shown in X, wherein X are halogen, R_fAnd R '_fIndependently selected from F, Cl or the perfluorinated alkyl with 1 to 10 carbon atom, a=0 to 2, b=0 to 1, and c=0 to 6；

B) step a) solution is merged to form reactant mixture in any order with nucleophilic compound Y and polar liquid；With

C) substantially all polymer solvents are removed from step b) reactant mixture to form dispersion by distilling, wherein the SO of about 5% to about 95%₂X side bases with nucleophilic compound Y react and about 95% to about 5% SO₂X side bases keep unreacted.

The polymer can be the homopolymer or copolymer of any configuration, such as block or random copolymer." fluorinated backbone " refers to that at least the 80% of halogen on polymer backbone and hydrogen atom sum is fluorine atom.The polymer can also be fluoridized, it means that the 100% of halogen on skeleton and hydrogen atom sum is fluorine atom.A type of suitable polymer is the first fluorinated vinyl monomer and with one or more SO₂The copolymer of second fluorinated vinyl monomer of X group.Possible first monomer includes tetrafluoroethene (TFE), hexafluoropropene, vinylidene fluoride, trifluoro-ethylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether and its mixture.Possible second comonomer includes various with SO₂The fluorinated vinyl ether of X group.X can be any halogen or the combination of more than one halogen, and usually F.

Suitable homopolymer and copolymer as known in the art include those described in WO 2000/0024709 and United States Patent (USP) 6,025,092.Commercially available suitable fluoropolymer is to come from E.I.du Pont de Nemours and Company, Wilmington DE

Fluoropolymer.It is a type of

Fluoropolymer is such as United States Patent (USP) 3, the copolymer of tetrafluoroethene (TFE) and perfluor (3,6- dioxa -4- methyl -7- octene sulfonyl fluorides) (PSEPVE) disclosed in 282,875.Other suitable fluoropolymers are such as United States Patent (USP) 4,358,545 and United States Patent (USP) No.4,940, the copolymer of TFE and perfluor (3- oxa- -4- pentenesulfonyl fluorides) (PSEVE) disclosed in 525, and the TFE and CF2=CFO (CF as disclosed in U.S. Patent application 2004/0121210₂)₄SO₂F copolymer.The polymer can include perfluoroparaffin (perfluorocarbon) skeleton and formula-O-CF₂CF(CF₃)-O-CF₂CF₂SO₂F side base.Such polymer is disclosed in United States Patent (USP) 3,282,875.Such as United States Patent (USP) 3, disclosed in 282,875, all these copolymers can be then by hydrolysis, generally by changing into ionomeric form in appropriate aqueous base.

The polymer is generally dissolved in polymer solvent with 1 to 30% (weight % or w/w) and preferably 10 to 20% (w/w) concentration first." polymer solvent " refers to the SO of polymer₂X-form dissolve and solvation and not otherwise with polymer reaction or the solvent of degradation polymer.Generally, polymer solvent is fluorination." fluorination " refers to that at least 10% of hydrogen and halogen atom sum in solvent is fluorine.The example of suitable polymer solvent includes but is not limited to, fluorocarbon (the only compound of carbon containing and fluorine atom), fluorohydrocarbon ether (fluorocarbon containing ehter bond in addition), HFC (compound of only carbon containing, hydrogen and fluorine atom), HFC ether (HFC containing ehter bond in addition), CFC (compound of only carbon containing, chlorine and fluorine atom), CFC ether (CFC containing ehter bond in addition), 2H- perfluors (5- methyl -3,6- dioxanonane) and

Electric liquid (3M, St.Paul, MN).Suitable solvent also includes the fluorated solvent from E.I.DuPont de Nemours (Wilmington, DE.).The mixture of one or more different polymer solvents can also be used.

By SO₂The polymer of X-form dissolves under agitation, and may require heating fully to dissolve.Solution temperature is likely to be dependent on polymer composition or the SO measured by equivalent (EW)₂X concentration.For the application, EW refer to neutralize 1 equivalent NaOH needed for sulphonic form polymer weight, with a gram/mol (g mol^-1) it is unit.High EW polymer (i.e. low SO₂X concentration) it may require higher solution temperature.When maximum dissolution temperature under atmospheric pressure is limited by solvent boiling point, suitable pressure vessel can be used to improve solution temperature.Polymer EW can be changed on demand for particular use.Here, being less than or equal to 1500 grams/mol of polymer usually using EW, more typically less than about 900 grams/mol.

Then, by the way that nucleophilic compound Y and polar liquid are mixed with polymer solution, reactive mixture is formed.Term " nucleophilic " and " nucleophile " are considered to belong to the chemical part with reactive electronics pair in the art.More specifically herein, nucleophilic compound Y can react replacement polymer SO by substituted type₂The halogen X of X group, and form covalent bond with sulphur.Suitable nucleophilic compound can include but is not limited to, water, alkali metal hydroxide, alcohol, amine, hydrocarbon and fluorocarbon sulfonamides.Nucleophilic compound Y addition is typically smaller than stoichiometric amount and determines the unreacted SO of holding₂The percentage of X group.

" polar liquid " refers to be under the process conditions any compound of liquid and refers to single liquid or the mixture of two or more polar liquids, and wherein one or more liquid have about 1.5 Debye units or higher, usual 2-5 dipole moment.More specifically, suitable polar liquid should be able to be by nucleophile Y, Y and polymer SO₂The reaction formation solvation of X group, but not necessarily by bulk polymer solvation.Suitable polar liquid includes but is not limited to dimethylformamide (DMF), dimethylacetylamide (DMAC), 1-METHYLPYRROLIDONE (NMP), dimethyl sulfoxide (DMSO), acetonitrile, propylene carbonate, methanol, ethanol, water or its combination.Suitable polar liquid preferably has the boiling point higher than polymer solvent.

Nucleophilic compound Y and polar liquid can be added in polymer solution in any order.Generally, nucleophile Y and part or all of polar liquid are added in polymer solution simultaneously as mixture.Additional polar liquid can be added in a separate step or different polar liquid.Other compounds can be added simultaneously or sequentially in any order with Y and polar liquid.For example, when y is water, non-nucleophilic base, such as, but not limited to LiH, NaH and NR can be added⁴R⁵R⁶, wherein R⁴、R⁵And R⁶It is optionally substituted alkyl or aryl.The polar liquid and nucleophile Y can also be identical compounds.In an example, when water had not only served as polar liquid but also served as nucleophile Y, it may be necessary to there is non-nucleophilic base as described above.

Nucleophilic compound and polar liquid are preferably added in polymer solution under fast turbulent mixing and at a temperature of close to solution temperature.When the dissolution temperature is low, polymer solution temperature can be improved before addition nucleophilic compound Y and polar liquid, usually above 50 DEG C.If this due to solvent, nucleophile Y or polar liquid boiling point and be restricted, suitable pressure vessel can be used to improve polymer solution temperature.The reaction --- wherein nucleophilic compound Y replacement polymers SO₂The halogen X of X group --- completed in 5 minutes to 2 hours generally after addition nucleophile and polar liquid.

Then, reactant mixture is distilled to remove essentially all of polymer solvent from the mixture.The distillation is preferably carried out under atmospheric pressure, but can be carried out under vacuo.When the boiling point or polar liquid of distillation still (still pot) temperature close to polar liquid start distillation, distillation is considered as completing.Traces of polymer solvent may be left after distillation.Distillation can be repeated once or more time, optionally on demand additional polar liquid to adjust viscosity.Residual reactant mixture is dispersion, wherein the SO of about 5% to about 95%₂X side bases with nucleophilic compound Y react and about 95% to about 5% SO₂X side bases keep unreacted.Preferably, the SO of about 25% to about 75%₂X side bases are reacted with nucleophilic compound Y, and the SO of about 75% to about 25%₂X side bases keep unreacted.The dispersion can also filter to remove insoluble matter." dispersion " refers to the homogeneous mixture of the physically stable of polymer fine particles in a solvent, that is, is not separated into separating the mixture of phase.

It is as described herein, when polar liquid is nucleophile Y and polymer pendant groups SO₂The good solvent of X reaction formation but when being not necessarily the solvent of bulk polymer, produce dispersion.SO₂The definite reaction formation of X group depends on nucleophile used.For example, when using in the water in the presence of non-nucleophilic base such as triethylamine (TEA), the reaction formation is three second ammonium sulfonate (SO₃ ^-TEAH⁺).Generally, side base is converted to SO₃M, wherein M are monovalent cations.

In another embodiment of the present invention, can be by formula HNR¹R²Compound be added to before the step of mention in the reactant mixture of (b) and (c) so that the residual SO of about 1% to about 100%₂X side bases change into SO₂NR¹R²Side base, wherein R¹And R²It independently is hydrogen or optionally substituted alkyl or aryl.Can be by the formula HNR that is added in reactant mixture¹R²Compound amount come control conversion SO₂The amount of X group.Suitable substituent includes but is not limited to ether oxygen (ether oxygens), halogen and amine function.Generally, R¹And R²It is hydrogen, alkyl or aryl alkyl.

Other aspects of the present invention are the polymeric dispersions being made up of any of the above described method and the film being made up of the dispersion.The preparation of film is discussed below.

In another embodiment, the new polymers dispersion of the polymer including one or more polar liquids and with fluorinated backbone is disclosed, the polymer includes about 5% to about 95%, preferably approximately 25% to about 75% such as formula-(O-CF₂CFR_f)_a-(O-CF₂)_b-(CFR’_f)_cSO₂Side base shown in Q and about 95% to about 5%, preferably approximately 75% to about 25% such as formula-(O-CF₂CFR_f)_a-(O-CF₂)_b-(CFR’_f)_cSO₃Side base shown in M, wherein Q are halogen or NR¹R²Or its mixture, R¹And R²It independently is hydrogen or optionally substituted alkyl, R_fWith R '_fIndependently selected from F, Cl or the perfluorinated alkyl with 1 to 10 carbon atom, a=0 to 2, b=0 to 1, c=0 to 6, and M are hydrogen or one or more monovalent cations.The polar liquid can be mixture and can be comprising at least one polar liquid, and can also include water as defined above.

The polymeric dispersions can use any conventional method formation film, such as, but not limited to solution or dispersion film casting technique.Film thickness can on demand change for specific electrochemical applications.Generally, film thickness is less than about 350 microns, more typically about 25 microns to about 175 microns.If desired, the film can be the laminated material of two kinds of polymer, such as two kinds of polymer with different EW.This film can be manufactured by being laminated two films.Or, one or both of the laminated material component can be by solution or dispersion cast.When the membrane is a laminate, in additional polymer monomeric unit chemical property can independently monomeric unit similar with first polymer property it is identical or different.It will be appreciated by those skilled in the art that the film being made up of dispersion can be used for packing, for non-electrochemical film purposes, as the thin polymer film and other typical uses of sheet material beyond the adhesive layer in multilayer film or sheet structure or other functional layers and electrochemistry.For the present invention, term " film " --- term commonly used in the art --- is synonymous with term " film " or " sheet material ", and they are term more often but refer to identical product.

The film can optionally include being used to improve mechanical performance, for reducing cost and/or porous carrier or reinforcement for other reasons.The porous carrier can be by multiple material, such as, but not limited to non-woven fabric or fabric, using various weaves, and such as plain weave, square flat weaving method, leno or other weaves are made.Porous carrier can be by glass, hydrocarbon polymer such as polyolefin (such as polyethylene, polypropylene), and perhalogenated polymer such as polychlorotrifluoroethylene is made.Porous, inorganic or ceramic material can also be used.Thermally and chemically degraded to be resistant to, the carrier is preferably by fluoropolymer, and most preferably perfluorinated polymers are made.For example, the (per) fluoropolymer of porous carrier can be polytetrafluoroethylene (PTFE) (PTFE) or tetrafluoroethene and CF₂=CFC_nF_2n+1(n=1 to 5) or (CF₂=CFO- (CF₂CF(CF₃)O)_mC_nF_2n+1(m=0 to 15, n=1 to copolymer 15) microporous membrane.Microporous PTFE film and sheet material are known, and they are suitable as carrier layer.For example, United States Patent (USP) 3,664,915 discloses the single axle drawn membrane with least 40% space.United States Patent (USP) 3,953,566,3,962,153 and 4,187,390 discloses the porous ptfe film with least 70% space.

The porous carrier or reinforcement can be incorporated to by being coated with above-mentioned polymeric dispersions on carrier so that the coating is distributed on the outer surface and by the internal void of carrier.Alternatively or additionally impregnate outer, thin film layer can be pressed onto on the one or both sides of porous carrier.When polar liquid dispersion is coated on relative non-polarity carrier such as microporous PTFE film, surfactant can be used to promote the wetting and close contact between dispersion and carrier.The carrier can pre-processed or can be added separately in dispersion with surfactant before being contacted with dispersion.It is preferred that surfactant be anionic fluorine-containing surfactant, such as from E.I.du Pont de Nemours and Company, Wilmington DE.Preferred fluorine-containing surfactant is

Figure 2007800203292100002G2007800203292D0008104806QIETU

1033D sulfonate.

The film being made up of above-mentioned dispersion can be by forming the method homogeneous cross-link of covalent bond between polymer pendant groups.A kind of method, which is included in before forming film, is added to crosslinkable in dispersion.These in this article refer to be possible to and SO₂The compound of X side bases formation crosslinking.The crosslinkable can also be formed in situ.The latter can be by by part or all of polymer SO₂X group, which is changed into, is possible to and adds or remain SO₂The functional group of X group reaction is carried out.Desirable crosslinkable is at least difunctionality, with two or more potential reaction groups, so that a group can react with a type of side base present on polymer.Other potential reaction groups in crosslinkable can react with the polymer pendant groups of identical or different type.Film be made and containing crosslinkable is then subjected to be conducive to the condition of crosslinking.

Suitable crosslinkable includes any molecule that can promote to be bonded with two or more side bases, includes but is not limited to, ammonia, diamines, carboxylic acid amides and sulfonamide.Crosslinking between polymer pendant groups generally comprises one or more sulfimide (- SO₂NHSO₂-) crosslinking.In one embodiment, ammonia is added in polymeric dispersions the residual SO so that 1% to 100% as crosslinkable₂X side bases change into sulfonamide (SO₂NH₂) side base.It is dispersions obtained can be with containing SO₂The additional dispersion mixing of X group, and pass through manufacture film of casting.High-temperature annealing step promotes the anhydrous condition in film in addition, and this is crucial in cross-linking process.Then the film is made to be subjected to promoting SO₂X side bases and SO₂NH₂The condition of cross-linking reaction between side base.Generally, this in the compound (being referred to as crosslinking accelerator) for can promote cross-linking reaction by carrying out.The example of crosslinking accelerator includes non-nucleophilic base.It is preferred that crosslinking accelerator be trialkylamine base, such as triethylamine, tripropyl amine (TPA), tri-n-butylamine and TEMED.Temperature equal or close to trialkylamine base boiling point is desirable for crosslinking.

In another crosslinking embodiment, it can be realized containing the crosslinking between the polymer pendant groups for having more than a sulfonimide moieties by adding single crosslinkable into dispersion.The compound can contain additional sulfonimide groups and/or at least two sulfuryl amine groups.A kind of suitable compound has formula HNR⁷SO₂R⁸SO₂NHR⁹, wherein R⁷And R⁹It independently is hydrogen or optionally substituted alkyl, and R⁸It is substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substitution sulfonimide polymer, ionene (ionene) polymer or substituted or unsubstituted heteroatom functional.The addition of this compound can promote to contain-SO₂NR⁷SO₂R⁸SO₂NR⁹SO₂The crosslinking of-part.Desirable such crosslinking is-SO₂NHSO₂(CF₂)₄SO₂NHSO₂-。

Still SO is contained₂The cross-linked polymer film of X group can be by using the hydrolysis of means known in the art into sulfonate radical (SO₃ ^-) form, this is sometimes referred to as ion or ionomeric form.For example, the film can convert it into sulfonic acid na form to hydrolyze by being impregnated in 25 weight %NaOH at about 90 DEG C about 16 hours and then the film being rinsed into (rinsing was using about 30 to about 60 minutes every time) twice in 90 DEG C of deionized waters.Another possible method is using 6-20% alkali metal hydroxides and the 5-40% polar organic solvents such as DMSO aqueous solution, the time of contact of at least 5 minutes at 50-100 DEG C, then rinses 10 minutes.After hydrolyzing, if it is desired, the film can be changed into another ionic species by making the film be contacted in the bath of the salting liquid containing required cation, or sour form is changed into by contacting and rinsing with acid such as nitric acid.For fuel cell applications, the film is usually sulphonic form.

Membrane electrode assembly (MEA) and the fuel cell being made from it are as known in the art and can include any of the above described film.There is described herein a kind of suitable embodiment.Using ionomeric polymer film by by its with comprising unsupported or load catalyst (such as platinum) on carbon particles, adhesive (such asFluoropolymer) and the catalyst layer of gas fusion backing merge and form MEA.Catalyst layer can be made up of known conductive catalytic active particle or material, and can manufacture by means commonly known in the art.Catalyst layer can be formed as the film of the polymer for the adhesive for serving as catalyst granules.Binder polymer can be the mixture of hydrophobic polymer, hydrophilic polymer or this kind of polymer.Binder polymer be typically ionomeric and can be and identical ionomer in film.Fuel cell by single MEA or multiple MEA of series stack by further providing for porous and conductive anode and cathode gas diffusion backings, the packing ring (it also provides electric insulation layer) at sealing MEA edges, the graphite current collector block in flow field is distributed with gas, is constituted with fuel cell is fixed on into aluminium end block, the cathode gas inlet of the anode inlet of fuel such as hydrogen and outlet, oxidant such as air and the outlet of pillar (tie rod) together.

Embodiment 1-8

Poly- (the co- TFE of PSEPVE-) and poly- (the co- TFE of PSEVE-) partial hydrolysis and dispersion are formed

Embodiment 1

By 52.3 grams poly- (the co- TFE of PSEPVE-), (it is tetrafluoroethene (TFE) and perfluor (3,6- dioxa -4- methyl -7- octene sulfonyl fluorides) (PSEPVE) copolymer, with 647 grams/mol of equivalents (80.8 mMs of SO₂F)) it is divided into aliquot and in dry 1 liter of 3 neck round bottom (RB) flask.The flask is furnished with mechanical agitation, heating mantles, the reflux condenser with nitrogen cushion, and thermocouple.About 185 milliliters of 2H- perfluors (5- methyl -3,6- dioxanonane) of addition (

E2) and by the polymer in the case where stirring and being heated to gentle reflux slow mechanism dissolved 0.5 hour.Reduce and heat and the solution is cooled to 50-70 DEG C.60 milliliters of DMFs (DMF) (about 320-RPM stirrings) are then slowly added to by syringe, translucent mixture is produced.Then solution of the syringe through 4.90 grams of (48.4 mMs) triethylamines (TEA) of addition in 5 minutes, 1.74 grams of water (96.7 mMs) and about 20 milliliters of DMF is passed through.After 10 minutes, white emulsion appearance is presented in the mixture.86 milliliters of DMF are added by syringe.The mixture is heated approximately at 80 to 90 DEG C in the case where continuously stirring (about 320-RPM) and kept at this temperature about 1 hour (h).Then reflux condenser is substituted for short path distilling apparatus.The emulsion is distilled under the slow nitrogen bubble through at the top of distillation still under atmospheric pressure.Distillate is collected under head temperature, the temperature starts at about 62 DEG C and rises to about 79 DEG C in distillation duration.Most of E2 is distillated, transparent almost colourless solution is left.It is about 230PPM to measure residual water by Karl Fisher (KF) titration.(about 60 DEG C, 29.5 "-Hg) are dried by press drying and then vacuum drying oven until realizing constant weight to measure solid weight percentage and be found to be 28.1%.With acetone-d₆Dispersion samples are diluted to about 5% (w/w).5% dispersion without with reference to (non-referenced)¹⁹F NMR show the residual SO in about 43.8-PPM₂F peaks (1F, integral area=32.9) and skeleton CF peaks (1F, integral area=100.0) in -139.9-PPM.Integral area calculating shows 67.1% SO₂F groups are hydrolyzed.

Embodiment 2

By 50.1 grams of poly- (the co- TFE of PSEPVE-) copolymer (77.4 mMs of SO with 648 grams/mol of equivalents₂F) it is divided into aliquot and in dry 500 milliliter of 3 neck round bottom (RB) flask.The flask is furnished with mechanical agitation, heating mantles and the reflux condenser with nitrogen cushion.Add about 175 milliliters

E2 and by the polymer under stirring and appropriate heating (50-60 DEG C) slow mechanism dissolved 1-2 hours.Under 320-RPM stirrings, 125 milliliters of DMF are slowly added to by syringe.Make the mixture uniform with most about 80 milliliters DMF.Further add DMF and provide white emulsion.Then 4.73 grams of (46.7 mMs) TEA are added by pipette, then adds about 1.85 grams of (103 mMs) water.The emulsion is heated to gentle reflux and kept at this temperature about 1.5 hours.Reduction is heated and the emulsion is cooled to below reflux temperature.Mechanical agitation is substituted for magnetic stirring and reflux condenser is substituted for short path distilling apparatus.The mixture is distilled under vacuum (230-mmHg), vapo(u)rizing temperature starts at about 55 DEG C and rises to about 79 DEG C in distillation duration.Most of E2 is distillated, transparent almost colourless solution is left.Additional 50 milliliters of E2 are simultaneously distillated subject to the foregoing, then add 25 milliliters of DMF to reduce viscosity.It is about 300 PPM to measure residual water by KF.(about 60 DEG C, 29.5 "-Hg) are dried by hot plate and subsequent vacuum drying oven until realizing constant weight to measure solid weight percentage and be found to be 27.7%.With acetone-d₆Dispersion samples are diluted to about 5% (w/w).5% dispersion without reference¹⁹F NMR show the residual SO in about 43.8-PPM₂F peaks (1F, integral area=35.7) and skeleton CF peaks (1F, integral area=100.0) in -139.9-PPM.Integral area calculating shows 64.3% SO₂F groups are hydrolyzed.

Embodiment 3

By 50.1 grams of poly- (the co- TFE of PSEPVE-) copolymer (77.3 mMs of SO with 648 grams/mol of equivalents₂F) it is divided into aliquot and in dry 500 milliliter of 3 neck round bottom (RB) flask.The flask is furnished with mechanical agitation, heating mantles and the reflux condenser with nitrogen cushion.Add about 175 milliliters

Figure 2007800203292100002G2007800203292D0011104944QIETU

E2 and by the polymer under stirring and appropriate heating (50-70 DEG C) slow mechanism dissolved about 1 hour.Solution is slowly added to about 75 milliliters of DMF in the case where about 50-70 DEG C and about 300-RPM is stirred by syringe.The mixture is colourless and translucent.Then 4.67 grams of (58.4 mMs) 50%NaOH aqueous solution were slowly added to through 5 to 10 minutes.Within a few minutes, the mixture starts that white emulsion appearance is presented.Add 100 milliliters of DMF and the mixture is heated to gentle reflux and kept at this temperature about 0.5 hour.Then stop heating and product being cooled to below reflux temperature.Mechanical agitation is substituted for magnetic stirring and reflux condenser is substituted for short path distilling apparatus.The mixture is distilled under vacuum (about 150-mmHg), vapo(u)rizing temperature starts at about 55 DEG C and rises to about 68 DEG C in distillation duration.Most of E2 is distillated, translucent pale yellow coloured dispersion is left.It is 0.26% to measure water by KF.Additional 100 milliliters of E2 are simultaneously distillated subject to the foregoing.Water is measured and for 0.093% by KF again.Use acetone-d₆Dilution 5% polymer solution without reference¹⁹F NMR show the residual SO in about 43.3-PPM₂F peaks (1F, integral area=44.6) and skeleton CF peaks (1F, integral area=100.0) in about -140-PPM.This SO equivalent to 55.4%₂F groups have been hydrolyzed.The dispersion is centrifuged, much transparent pale yellow coloured dispersion and about 4 to 5 milliliters white depositions are left, this seems NaF.(about 80 DEG C, 29.5 "-Hg) are dried by vacuum drying oven until realizing constant weight to measure solid weight percentage and be found to be 26.4%.

Embodiment 4

By 50.09 grams of (69.8 mMs of SO₂F) poly- (the co- TFE of the PSEPVE-) copolymer with 718 grams/mol of equivalents is divided into aliquot and in 500 milliliter of 3 neck RB flask.The flask is furnished with mechanical agitation, heating mantles and the reflux condenser with nitrogen cushion.Add about 175 milliliters of E2 and by the polymer under gentle reflux stirring slow mechanism dissolved about 3 hours.Reduce and heat and cool the temperature to about 70-90 DEG C.Under 350-RPM stirrings, 1.41 grams of (14.0 mMs) TEA, 0.50 gram of water and 45 grams of DMF solution are slowly added to using 125 milliliters of pressure equalizing addition funnels.The solution becomes translucent after charging.104 grams of DMF are added by funnel, white emulsion appearance is presented in the mixture.The emulsion is stirred for 1 hour at about 70-90 DEG C.Stop heating and product being cooled to below reflux temperature.Condenser is substituted for nitrogen bubbler and charging hopper is changed into short path distilling apparatus.The white emulsion is distilled under nitrogen bubble under atmospheric pressure, and is slowly changed into transparent and almost colourless with E2 is removed.It is about 260PPM to measure residual water by KF.(about 60 DEG C, 29.5 "-Hg) are dried by hot plate and subsequent vacuum drying oven until realizing constant weight to measure solid weight percentage and be found to be 28.3%.With acetone-d₆Dispersion samples are diluted to about 5% (w/w).5% dispersion without reference¹⁹FNMR shows the residual SO in about 44-PPM₂F peaks (1F, integral area=11.1) and with two side base-OCF₂- and-CF₃The corresponding complicated peak span -70 to -90PPM of resonating (7F, integral area=100.0).Integral area calculating shows 22.3% SO₂F groups are hydrolyzed.

Embodiment 5

By 50.0 grams of (55.7 mMs of SO₂Poly- (the co- TFE of the PSEPVE-) copolymer F) with about 850 grams/mol of equivalents is mounted in drying

In 5100 glass reactors.The reactor is evacuated and 220 milliliters are added by conduit

E2.The reactor is backfilled with N2 and atmospheric pressure is vented to.By a few houres dissolving under reactor is heated into 125 DEG C and stirs pill 700 to 1000RPM.Use Waters

HPLC pumps are slowly added to solution (22.3 mM TEAs, 44.6 mM water) of the TEA of (1 ml/min) 22.6 milliliter of 0.100 grams per milliliter in DMF.Maximum reactor pressure is 20PSIG.Other 120 milliliters of DMF (2 ml/min) are pumped into reactor, white emulsion appearance is presented in the reactant mixture.The emulsion is cooled to<40 DEG C, it is then transferred into equipped with mechanical agitation, short path distilling apparatus and N₂In 1 liter of 3 neck RB flask of bubbling.The emulsion is distilled under atmospheric pressure.With removing major part E2 and forming dispersion, the emulsion is changed into translucent, nearly transparent.90 milliliters of DMF are added in still-process to reduce viscosity.After cooling to ambient temperature, the nearly transparent dispersion is filtered by polypropylene filter cloth.(about 60 DEG C, 29.5 "-Hg) are dried by hot plate and subsequent vacuum drying oven until realizing constant weight to measure solid weight percentage and be found to be 18.6%.With acetone-d₆Dispersion samples are diluted to about 5% (w/w).5% dispersion without reference¹⁹F NMR show the residual SO in about 43-PPM₂F resonance (1F, integral area=1.59) and centered on about -82PPM and with side base CF₃With two-OCF₂The corresponding broad peak of-resonance (7F, integral area=20.0).Integral area calculating shows 44.4% SO₂F groups are hydrolyzed.By -82PPM resonance integrals area and total mark area (not including SO₂F ratio), calculates equivalent (SO₂F forms) it is 855 grams/mol.

Embodiment 6

By 25.05 grams of (50.6 mMs of SO₂F) poly- (the co- TFE of PSEVE-) (it is the copolymer of tetrafluoroethene (TFE) and perfluor (3- oxa- -4- pentenesulfonyl fluorides) (PSEVE), the EW with 495 grams/mol) is divided into aliquot and in 500 milliliter of 3 neck RB flask.The flask is furnished with mechanical agitation, heating mantles and the reflux condenser with nitrogen cushion.Add about 88 milliliters

E2 and by the polymer under gentle reflux stirring slow mechanism dissolved about 1 hour.Reduction is heated and the solution is cooled into 70 to 90 DEG C.Under stirring (about 320-RPM) rapidly, using 125 milliliters of pressure equalizing addition funnels through being slowly added within about 15 minutes the hydrating solution being made up of 0.770 gram of TEA (7.61 mMs), 0.274 gram of water (15.2 mMs) and about 28 grams of DMF.The mixture is uniform and translucent.Slowly additional 110 grams of DMF, and produce white emulsion.Enhancing heating and by the emulsion gentle reflux about 0.5 hour.Then stop heating and emulsion being cooled to below reflux temperature.Condenser is substituted for nitrogen bubbler and charging hopper is substituted for short path distilling apparatus.The emulsion is distilled under gentle nitrogen sparge under atmospheric pressure, and is slowly changed into transparent and almost colourless with E2 is removed.After cooling to ambient temperature, the dispersion is filtered by polypropylene filter cloth.It is about 520PPM to measure residual water by KF.(about 60 DEG C, 29.5 "-Hg) are dried by hot plate and subsequent vacuum drying oven until realizing constant weight to measure solid weight percentage and be found to be 17.2%.With acetone-d₆Dispersion samples are diluted to about 5% (w/w).5% dispersion without reference¹⁹FNMR shows the residual SO in about 44-PPM₂F peaks (1F, integral area=3.50) and wide side base-OCF₂- resonance about -82PPM (2F, integral area=10.00).Integral area calculating shows 30.0% SO₂F groups are hydrolyzed.

Embodiment 7

By 50.06 grams of (101 mMs of SO₂F) poly- (the co- TFE of PSEVE-) copolymer (EW=495 grams/mol) is divided into aliquot and in 1 liter of 3 neck RB flask.The flask is furnished with mechanical agitation, heating mantles and the reflux condenser with nitrogen cushion.Add about 175 milliliters of E2 and by the polymer under gentle reflux stirring slow mechanism dissolved about 1 hour.Reduction is heated and the solution is cooled into 70 to 90 DEG C.Under stirring (about 320-RPM) rapidly, using 125 milliliters of pressure equalizing addition funnels through being slowly added within about 15 minutes the hydrating solution being made up of 2.04 grams of TEA (20.2 mMs), 0.727 gram of water (40.4 mMs) and about 36 grams of DMF.The mixture is uniform and translucent.Slowly additional 85 grams of DMF, and white emulsion appearance is presented in the mixture.The emulsion is heated to gentle reflux and kept at this temperature about 0.5 hour.Then stop heating and the product being cooled to below reflux temperature.Condenser is substituted for nitrogen bubbler and charging hopper is substituted for short path distilling apparatus.The white emulsion is distilled under nitrogen bubble under atmospheric pressure, and is slowly changed into transparent and light yellow with E2 is removed.It is about 170PPM to measure residual water by KF.(about 60 DEG C, 29.5 "-Hg) are dried by hot plate and vacuum drying oven until realizing constant weight to measure solid weight percentage and be found to be 27.2%.With acetone-d₆Dispersion samples are diluted to about 5% (w/w).5% dispersion without reference¹⁹F NMR show the residual SO in about 44-PPM₂F peaks (1F, integral area=6.17) and in about -82PPM wide side base-OCF₂- resonance (2F, integral area=17).Integral area calculating shows 27% SO₂F groups are hydrolyzed.

Embodiment 8

By 25.0 grams of (42.2 mMs of SO₂F) poly- (the co- TFE of PSEVE-) copolymer (EW=593 grams/mol) is divided into aliquot and in 500 milliliter of 3 neck RB flask.The flask is furnished with mechanical agitation, heating mantles and the reflux condenser with nitrogen cushion.Add about 175 milliliters

Figure 2007800203292100002G2007800203292D0014105211QIETU

E2 and by the polymer under gentle reflux stirring slow mechanism dissolved about 1 hour.Reduction is heated and the solution is cooled into 70 to 90 DEG C.Under stirring (about 320-RPM) rapidly, 1.30 grams of (12.8 mMs, 0.303 equivalent) TEA, 0.46 gram of DI water and about 19 grams of DMF solution is slowly added to using 125 milliliters of pressure equalizing addition funnels.The solution is changed into translucent after charging.95 grams of DMF are added by funnel, white emulsion appearance is presented in the mixture.The mixture is stirred for 0.5 hour at this temperature.Then stop heating and the product being cooled to below reflux temperature.Condenser is substituted for nitrogen bubbler and charging hopper is substituted for short path distilling apparatus.The white emulsion is distilled under nitrogen bubble under atmospheric pressure.With major part E2 is removed, the dispersion is nearly transparent.It is cooled to after room temperature, the dispersion is filtered by polypropylene filter cloth.Repeating part is hydrolyzed in substantially the same manner, and merges two products.(about 60 DEG C, 29.5 "-Hg) are dried by hot plate and vacuum drying oven until realizing constant weight to measure solid weight percentage and be found to be 18.0%.With acetone-d₆Dispersion samples are diluted to about 5% (w/w).5% dispersion without reference¹⁹F NMR show the residual SO in about 44-PPM₂F resonance (1F, the wide side base-OCF of integral area=3.37) and centered on about -82PPM₂- (2F, integral area=10.0) resonate.Integral area calculating shows 32.6% SO₂F groups are hydrolyzed.

Embodiment 9-10

Pass through dispersion SO₂F groups are to sulfonamide (SO₂NH₂) group is converted to form cross-linking dose

Embodiment 9

By 91.8 grams of (12.8 mMs of SO₂F the dispersion) from embodiment 2 is mounted in 250 milliliter of 3 neck RB flask of drying equipped with mechanical agitation, the dry-ice condenser with nitrogen cushion and gas addition port.Flask contents are cooled to about 5 DEG C using ice-water bath.1.04 grams of (61.1 mMs) ammonia are added with the speed of 120 to 130 mg minutes using mass flow integrator.As ammonia is added, the mixture becomes muddy.Flask contents are stirred 0.5 hour at a temperature of ice-water bath.Remove and bathe and flask contents are risen into ambient temperature overnight under agitation.Remove dry-ice condenser and ammonia charge door and be substituted for nitrogen pad adapter, short path distilling apparatus and heating mantles.Add about 6 milliliters of TEA and heat the RB flasks under stirring and gentle nitrogen sparge to realize ammonium cation to the conversion of three second ammonium cations.The cloudy dispersion begins to change into transparent at about 70 DEG C and is light yellow.Stop heating when not regathering residual TEA in observing reception flask.(about 60 to 90 DEG C, 29.5 "-Hg) are dried by vacuum drying oven until realizing constant weight to measure solid weight percentage and be found to be 31.1%.By by dispersion cast into film¹⁹F NMR and FTIR spectrum method confirm residual SO₂The disappearance of F groups and SO₂NH₂The presence of group.Confirm with about 3200-cm^-1Centered on NH absorb and in about 1470-cm^-1Under residual SO₂The disappearance that F absorbs.

Embodiment 10

By 75 grams of dispersion (9.71 mMs of SO from embodiment 1₂F) it is mounted in 250 milliliter of 3 neck RB flask of drying equipped with mechanical agitation, the dry-ice condenser with nitrogen cushion and ammonia charge door.Flask contents are cooled to about 5 DEG C using ice-water bath.0.65 gram of (38.2 mMs) ammonia is added with the speed of 120 to 130 mg minutes using mass flow integrator.As ammonia is added, the mixture becomes muddy.Flask contents are stirred 0.5 hour at a temperature of ice-water bath.Remove and bathe and flask contents were risen into environment temperature through 2 to 3 hours under agitation.Remove dry-ice condenser and ammonia charge door and be substituted for nitrogen pad adapter, short path distilling apparatus and heating mantles.Add about 6 milliliters of TEA and heat the RB flasks under stirring and gentle nitrogen sparge to realize ammonium cation to the conversion of three second ammonium cations and except deammoniation and excess TEA.The cloudy dispersion begins to change into transparent at about 70 DEG C and is light yellow.Stop heating when not regathering residual TEA in observing reception flask.Once being cooled to environment temperature, (about 60 to 90 DEG C, 29.5 "-Hg) are dried by vacuum drying oven until realizing constant weight to measure solid weight percentage and be found to be 28.3%.By by dispersion cast into film¹⁹FNMR and FTIR spectrum method confirm residual SO₂The disappearance of F groups and SO₂NH₂The presence of group.Confirm with about 3200-cm^-1Centered on NH absorb and in about 1470-cm^-1Under residual SO₂The disappearance that F absorbs.

Embodiment 11-14

Film manufacture, crosslinking and hydrolysis acid are exchanged

Embodiment 11

Prepare the mixture being made up of the polymeric cross-linker of the dispersion in 3 parts by weight of example 2 and 2 parts by weight of example 9.Using the scraper with 0.025 " gap in 2 mil thicks

By the mixture cast membrane on (pasting on glass).

Figure 2007800203292100002G2007800203292D0017154256QIETU

Film on/glass on horizontal hot plate mild heat (about 50 DEG C) to evaporate DMF.Then by the film from removed on glass and in forced air draft oven at 150 DEG C by being further dried/annealing steps 5 minutes.Film thickness after annealing is 74 ± 2 microns.Two piece of 46 mm dia circular specimen is cut from the film.

Backing still in the original location in the case of, one of sample is passed through cross-linking step, wherein by its under gentle reflux in 15 milliliters of anhydrous organic base N, N, N ', dipping 3 hours in N '-tetramethylethylenediamine (TMEDA).Two samples are then made all to pass through hydrolysing step, wherein each sample is individually mounted on containing 40 milliliters of 23-% (w/w) potassium hydroxide in water/ethanol (4:1) in 125 milliliters of conical flasks of the solution in.In heating, the sample Jing Guo cross-linking step is not disperse easily in hydrolysed mix, is left

Backed film.Under hydrating solution backflow, sample by crosslinking with

Backed film is separated, and is slightly swelled, but still keeps complete.The exchange of two hypo acids is further imposed to crosslinked film in concentrated nitric acid, finally washing lotion pH value >=6 until being measured using general pH test paper are rinsed with deionized water.A diameter of 50 ± 1 millimeters of the film of water immersion, and thickness is 88 ± 2 microns.Measurement EW is dried and for 725 grams/mol by titration and vacuum drying oven.

Embodiment 12

Poly- (the co- TFE of the PSEPVE-) dispersion of the partial hydrolysis of 55.35 grams of embodiments 4 is added to in 250 milliliters of RB flasks that are septate clean and drying.Under magnetic stirring and ice bath cooling, 4.57 grams of 1.99% ethylenediamine (EDA) solution (1.52 mMs) in DMF is slowly added to using 5 cubic centimetres of glass syringes.Ice bath is removed after EDA additions, and dispersion is stirred 1 hour, while being warmed to environmental condition.The dispersion is filtered using~10 micron polypropylene filter cloths and using the casting knife with 0.020 " gap in 2 mil thicks

Cast membrane on (pasting on glass).

Wet film on/glass on horizontal hot plate mild heat (about 50 DEG C) to evaporate DMF.Then removed from glass

On dry film and in forced air draft oven at 150 DEG C by being further dried/annealing steps 5 minutes.Thickness of dry film is about 50 microns.Two piece of 46 mm dia circular specimen is cut from the film.

Backing still in the original location in the case of, one of sample is passed through cross-linking step, wherein being immersed in 15 milliliters of TMEDA and gentle reflux 3 hours.Two samples are then made all to pass through hydrolysing step, wherein each sample is individually mounted on containing 40 milliliters of 23-% (w/w) potassium hydroxide in water/ethanol (4:1) in 125 milliliters of conical flasks of the solution in.In heating, the sample parts dissolving not Jing Guo cross-linking step shows that certain crosslinking occurs in annealing process.Under hydrating solution backflow, sample by crosslinking with

Backing UF membrane, is slightly swelled, but still keeps complete.The exchange of two hypo acids is further imposed to crosslinked film in concentrated nitric acid, finally washing lotion pH value >=6 until being measured using general pH test paper are rinsed with deionized water.

Embodiment 13

By 5.51 grams of (1.64 mMs of SO₂F) poly- (the co- TFE of the PSEPVE-) dispersion and 0.265 gram of (0.736 mM) NH of the partial hydrolysis of embodiment 4₂SO₂(CF₂)₄SO₂NH₂It is added in 20 cubic centimetres of dry vials.The NH₂SO₂(CF₂)₄SO₂NH₂It is readily dissolved under magnetic stirring in dispersion.By the way that dispersion is poured on into 2 mil thicks

(pasting on glass) comes up cast membrane.

Film on/glass on horizontal hot plate mild heat (about 50 DEG C) to evaporate DMF.Then removed from glass

On dry film and in forced air draft oven at 150 DEG C by being further dried/annealing steps 5 minutes.Dry film is fully transparent and thickness is about 100 microns.Excess is trimmed from the film of annealing

And backing in the original location in the case of, by the way that a few houres crosslink reaction under backflow TMEDA on LiH.Then the film is used into 23-% (w/w) potassium hydroxide in water/ethanol (4:1) solution in hydrolyse over night at ambient temperature.After hydrolyzing, easily remove

Backing.Film acid in 35% nitric acid of backflow is exchanged 2 hours.Then the film is rinsed with deionized water, then exchanged with 2M HCl acid, finally rinsed with deionized water.Small film sample is titrated and equivalent is 770 grams/mol.

Embodiment 14

By 50.0 grams of (9.70 mMs of SO₂F) poly- (the co- TFE of the PSEVE-) dispersion and 1.16 grams of (3.22 mMs) NH of the partial hydrolysis of embodiment 8₂SO₂(CF₂)₄SO₂NH₂It is added in 250 milliliters of dry RB flasks.The NH₂SO₂(CF₂)₄SO₂NH₂It is readily dissolved under magnetic stirring in the dispersion.Then the homogeneous mixture is passed through into the filtering of~10 micron polypropylene filter cloths.By 8 " × 10 " mould surfaces with pasting (water tacked) to 2 mils in substrate of glass with water

Film is assembled.The substrate of glass is placed on the aluminium sheet using small hot plate mild heat (~50 DEG C).Should

, substrate of glass, aluminium sheet and hot plate assembly be placed on reconcilable loading floor and smooth.Meanwhile, 10 " diameter circular sample loads of 0.001 " thick expanded microporous polytetra fluoroethylene-EPTEE (ePTFE) are used in combination on hoop (embroidery hoop)

1033D 0.5-% (w/v) triethylammonium salts solution spraying in ethanol.The ethanol evaporation under dry nitrogen stream.

7 " the wide casting knifes with adjustable blade are installed with 0.008 " gap.The casting knife is placed on the table top from rear end forward about 0.75 ".About 6 milliliters of dispersion mixtures are carefully placed on and (avoid entrained air bubbles) in the space by curtain coating blade and lateral carrier delimitation on table top.Then knife is pulled along towards table top front end.The ePTFE being made is placed in table top center, and the dispersion is immersed substrate.Remove hoop and the cover with dry nitrogen bubble entrance and exit is placed on whole table top assembly.After 1h, the film sufficiently dry and with first layer substantially similar way apply the second dispersion layer.The shield on whole assembly is changed, and restarts dry nitrogen bubble.Film efficient drying after~1 hour.Remove and remain adhered to from casting knife

On film and in forced air draft oven at 150 DEG C anneal 2 minutes.Then by the film from

Figure 2007800203292100002G2007800203292D0019154724QIETU

Divest and be supported in 6.5 " diameter stainless steel hoops on backing.

The film water of load is lain in 8 " the shallow diameter kettles equipped with reflux condenser and dry nitrogen cushion.The film on LiH under backflow TMEDA steams by being crosslinked.Film surface is away from backflow TMEDA about 1 ".Stop cross-linking step after 1h.Then by the film of load in the 15%KOH aqueous solution at 70 to 90 DEG C hydrolyze 30 minutes, then wash excessive KOH off using deionized water.By the film of load 2M HNO₃Acid is exchanged 30 minutes, and excess acid is then washed with deionized water.Use 35%HNO₃Quadratic acid is carried out under reflux to exchange 30 minutes.Finally, the film is rinsed with deionized water, uses 2M HNO₃Acid is exchanged, and is rinsed with deionized water, then the air dried overnight before being removed from hoop.Thickness of dry film is 35 microns.

Claims

1. manufacturing the method for polymeric dispersions, comprise the following steps：

A) provide comprising polymer solvent and contain SO₂The solution of the polymer of X side bases, the wherein polymer are comprising fluorinated backbone and by formula-(O-CF₂CFR_f)_a-(O-CF₂)_b-(CFR’_f)_cSO₂Side base shown in X, wherein X are halogen, R_fAnd R '_fIndependently selected from F, Cl or the perfluorinated alkyl with 1 to 10 carbon atom, a=0 to 2, b=0 to 1, and c=0 to 6；

B) step a) solution is merged to form reactant mixture with nucleophilic compound Y and polar liquid；With

C) substantially all polymer solvents are removed from step b) reactant mixture to form dispersion by distilling, wherein 5% to 95% SO₂X side bases with nucleophilic compound Y react and 95% to 5% SO₂X side bases keep unreacted；

Wherein described polymer solvent refers to the SO of polymer₂X-form dissolve and solvation and not otherwise with polymer reaction or the solvent of degradation polymer, and the nucleophilic compound Y can pass through substituted type reaction replacement polymer SO₂The halogen X of X group, and form covalent bond with sulphur.

2. the method for claim 1 wherein in step b), before merging with step a) solution, polar liquid and nucleophilic compound Y are mixed.

3. the method for claim 1 wherein in step c), 25% to 75% SO₂X side bases with nucleophilic compound Y react and 75% to 25% SO₂X side bases keep unreacted.

4. the method for claim 1, it is comprised additionally in formula HNR¹R²Compound be added to step in the dispersion formed in step c) so that 1% to 100% residual SO₂X side bases change into SO₂NR¹R²Side base, wherein R¹And R²It independently is hydrogen or optionally substituted alkyl or aryl.

5. the method for claim 1 wherein polar liquid is selected from DMF, DMAC, NMP, DMSO, acetonitrile, propylene carbonate, methanol, ethanol, water or its combination.

6. the method for claim 1 wherein X is F.

7. the method for claim 1 wherein polymer solvent is fluorination.

8. the method for claim 6, wherein polymer solvent are selected from fluorocarbon, fluorohydrocarbon ether, HFC, HFC ether, CFC, CFC ether, 2H- perfluors (5- methyl -3,6- dioxanonane) or its any combinations.

9. the method for claim 1 wherein nucleophilic compound Y is water and the water is mixed with non-nucleophilic base.

10. the method for claim 9, wherein non-nucleophilic base are selected from LiH, NaH and NR⁴R⁵R⁶, wherein R⁴、R⁵And R⁶It is optionally substituted alkyl.

11. the method for claim 1 wherein nucleophilic compound Y is selected from LiOH, NaOH, KOH, CsOH and its any combinations.

12. the method for claim 1 wherein in step c), SO₂X side bases are reacted into SO₃M, wherein M are monovalent cations.

13. the method for claim 1 wherein step a) polymer includes formula-O-CF₂CF(CF₃)-O-CF₂CF₂SO₂F or-OCF₂CF₂SO₂F side base, or its any combinations.

14. the method for claim 13, wherein step a) polymer is fluoridized.

15. the dispersion as made from the method for claim 1.

16. the dispersion as made from the method for claim 4.

17. the film prepared by the dispersion of claim 15.

18. the film of claim 17, wherein the film is the introduction of the enhancing film of the reinforcing material of expansion, micropore or fibril.

19. the film prepared by the dispersion of claim 16.

20. the film of claim 19, wherein the film is the introduction of the enhancing film of the reinforcing material of expansion, micropore or fibril.

21. manufacturing the method for film, comprise the following steps：

B) step a) solution is merged to form reactant mixture with nucleophilic compound Y and polar liquid；

C) substantially all polymer solvents are removed from step b) reactant mixture to form dispersion by distilling, wherein 5% to 95% SO₂X side bases with nucleophilic compound Y react and 95% to 5% SO₂X side bases keep unreacted；With

D) film is prepared by step c) dispersion；

22. the method for claim 21, the step of also being mixed including the reactant mixture for making step b) or step c) dispersion with crosslinkable.

23. the method for claim 21, wherein in step c), 25% to 75% SO₂X side bases with nucleophilic compound Y react and 75% to 25% SO₂X side bases keep unreacted.

24. the method for claim 22, wherein the crosslinkable is formula HNR¹R²Compound, and in step c) 1% to 100% residual SO₂X side bases change into SO₂NR¹R²Side base, wherein R¹And R²It independently is hydrogen or optionally substituted alkyl.

25. the method for claim 21, comprises additionally in the film for making step d) and crosslinking accelerator contacts to form the step of being crosslinked between side base.

26. the method for claim 25, wherein the crosslinking includes one or more sulfonimide moieties.

27. the method for claim 26, wherein the sulfonimide moieties include NR⁷R⁸SO₂R⁹SO₂NR¹⁰R¹¹, wherein R⁷、R⁸、R¹⁰And R¹¹It independently is hydrogen or optionally substituted alkyl, and R⁹It is substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substitution sulfonimide polymer, ionene polymer or substituted or unsubstituted heteroatom functional.

28. the method for claim 21, the step of reinforcing material is introduced into step c) dispersion when wherein step d) is included in preparation process d) film, and comprise additionally in the film for making step d) and the step of crosslinking accelerator contact to form crosslinking between side base.

29. the method for claim 21, wherein polar liquid are selected from DMF, DMAC, NMP, DMSO, acetonitrile, propylene carbonate, methanol, ethanol, water or its combination.

30. the method for claim 21, wherein X are F.

31. the method for claim 21, wherein polymer solvent are fluorinations.

32. the method for claim 31, wherein polymer solvent are fluorocarbon, fluorohydrocarbon ether, HFC, HFC ether, CFC, CFC ether, 2H- perfluors (5- methyl -3,6- dioxanonane) or its combination.

33. the water of the method for claim 21, wherein nucleophilic compound Y right and wrongs nucleophilic alkali mixing, wherein the non-nucleophilic base is selected from LiH, NaH and NR⁴R⁵R⁶, wherein R⁴、R⁵And R⁶It is optionally substituted alkyl.

34. the method for claim 21, wherein nucleophilic compound Y are selected from LiOH, NaOH, KOH, CsOH or its combination.

35. the method for claim 21, wherein in step c), SO₂X side bases have changed into SO₃M, wherein M are monovalent cations.

36. the method for claim 21, wherein step a) polymer include fluorination or perfluorinated backbone and formula-O-CF₂CF(CF₃)-O-CF₂CF₂SO₂F or-OCF₂CF₂SO₂F or its any combination of side base.

37. the film prepared by the method for claim 21.

38. the film prepared by the method for claim 24.

39. the method for claim 1 wherein the nucleophilic compound Y is amine.